Ta-doped Li7La3Zr2O12 (LLZTO) solid-state electrolytes (SEs) show great promise for solid-state batteries due to its high conductivity and safety. However, one of the challenges it faces is lithium dendrite propagation upon long-term cycling. To address this issue, we propose the incorporation of fumed silica (FS) at the grain boundaries of LLZTO to modify the properties of the garnet pellet, which effectively inhibits the dendrite growth. The introduction of FS has demonstrated several beneficial effects. Firstly, it reduces the migration barrier of lithium ions, which helps prevent dendrite formation and propagation. Additionally, FS reduces the electronic conductivity of the SEs pellet, suppressing the dendrite formation. Moreover, the formed lithium silicates from FS might also be acted as electron inhibitor, thus inhibiting the lithium dendrite growth upon cycling. By investigating the use of FS as a modifier in LLZTO-based electrolytes, our study contributes to advancing dendrite-free solid-state electrolytes and thus the development of high-performance all-solid-state batteries.

The Li3MX6 compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li3ScCl6 using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P63mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li3ScCl6 and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li3MX6 family further revealed that the cation/anion radius ratio, rM/rX, is the factor that determines which anion sublattice is formed and that in γ-Li3ScCl6, the difference in compressibility between Sc and Cl exceeds the ccp rM/rX threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li3ScCl6 demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings.

The development of Li-ion conducting solid-state electrolytes (SSEs) is crucial to achieve increased energy density, operative reliability, and unprecedented safety to replace the state-of-the-art Li-ion battery (LIB). In this regard, we here present the successful melt-casting synthesis of a MgO-added NASICON-type LAGP glass-ceramic electrolyte with composition Li1.5Al0.3Mg0.1Ge1.6(PO4)3, namely LAMGP. The effects of three different additional oxides are investigated, with the aim to improve grain cohesion and consequently enhance Li-ion conductivity. Specifically, yttrium oxide (Y2O3, 5 mol%), boron oxide (B2O3, 0.7 mol%) and silicon oxide (SiO2, 2.4 %mol) are added, yielding LAMGP-Y, LAMGP-B and LAMGP-Si, respectively. Their effects are exhaustively compared in terms of thermal, crystalline, structural/morphological and ion conducting features. Among the three oxides, B2O3 is able to positively act on grain boundaries without bringing along grains deformation and insulating secondary phases formation, achieving enhanced ionic conductivity of 0.21 mS cm-1 at 20 °C as compared to 0.08 mS cm-1 for a commercial LAGP subjected to the same thermal treatment. A remarkable anodic oxidation stability up to 4.8 V vs Li+/Li is assessed by LAMGP-B system, which accounts for promising prospects for its use in combination with high-energy (high-V) cathodes.

Li7La3Zr2O12 (LLZO) is one of the most promising candidate solid electrolytes for high-safety solid-state batteries. However, similar to other solid electrolytes containing volatile components during high-temperature sintering, the preparation of densified LLZO with high conductivity is challenging involving the complicated gas-liquid-solid sintering mechanism. Further attention on establishing low-cost laborastory-scale preparation craft platform of LLZO ceramic is also required. This work demonstrates a \"pellet on gravel\" sintering strategy, which is performed in a MgO crucible and box furnace under ambient air without any special equipment or expensive consumables. In addition, the competition between lithium loss from the sintering system and internal grain densification is critically studied, whereas the influences of particle surface energy, Li-loss amount, and initial excess Li2O amount are uncovered. Based on the sintering behavior and mechanism, optimized craft platform for preparing dense LLZO solid electrolytes including mixing, calcination, particle tailoring and sintering is provided. Finally, exemplary Ta-doped LLZO pellets with 2 wt % La2Zr2O7 additives sintered at 1260-1320 °C for 20 min deliver Li+ conductivities of ∼9 × 10-4 S cm-1 at 25 °C, relative densities of >96%, and a dense cross-sectional microstructure. As a practical demonstration, LLZO solid electrolyte with optimized performance is applied in both Li-Li symmetric cells and Li-S batteries. This work sheds light on the practical production of high-quality LLZO ceramics and provides inspiration for sintering ceramics containing volatile compounds.

Solid-state batteries (SSBs) are promising candidates to significantly exceed the energy densities of today\'s state-of-the-art technology, lithium-ion batteries (LIBs). To enable this advancement, optimizing the solid electrolyte (SE) is the key. β-Li3 PS4 (β-LPS) is the most studied member of the Li2 S-P2 S5 family, offering promising properties for implementation in electric vehicles. In this work, the microstructure of this SE and how it influences the electrochemical performance are systematically investigated. To figure this out, four batches of β-LPS electrolyte with different particle size, shape, and porosity are investigated in detail. It is found that differences in pellet porosities mostly originate from single-particle intrinsic features and less from interparticle voids. Surprisingly, the β-LPS electrolyte pellets with the highest porosity and larger particle size not only show the highest ionic conductivity (up to 0.049 mS cm-1 at RT), but also the most stable cycling performance in symmetrical Li cells. This behavior is traced back to the grain boundary resistance. Larger SE particles seem to be more attractive, as their grain boundary contribution is lower than that of denser pellets prepared using smaller β-LPS particles.

NASICON-type oxide Li1+xAlxTi2-x(PO4)3 (LATP) is expected to be a promising solid electrolyte (SE) for all-solid-state batteries (ASSBs) owing to its high ion conductivity and chemical stability. However, its interface properties with electrodes on the atomic scale remain unclear, but it is crucial for rational control of the ASSBs performance. Herein, we focused on the LATP SE with x = 0.17 and investigated the electron and ion transfer behaviors at the interfaces with the Li metal negative electrode and the LiCoO2 (LCO) positive electrode via explicit interface models and density functional theory calculations. Ti reduction was found at the LATP/Li interface. For the LATP/LCO interface, the results indicated the Li-ion transfer from LCO to LATP upon contact until a certain electric double layer is formed under equilibrium, in which LCO is partially reduced. Co-Ti exchange was also found to be favorable where the Li ion moves with Co3+ to LATP. We also explored the possible interfacial processes during annealing by simulating the oxygen removal effect and found that oxygen vacancy can be more easily formed in the LCO at the interface. It implies that partial Li ions move back to LCO for the local charge neutrality. We also demonstrated higher Li chemical potential around the LATP/LCO interfaces, leading to the dynamical Li-ion depletion upon charging. The calculation results and the deduced mechanisms well explain the experimental results so far and provide insights into the interfacial electron and ion transfer upon contact, during annealing, and charging.

The title compounds exhibit a K2NiF4-type layered perovskite structure; they are based on the La1.2Sr0.8InO4+δ oxide, which was found to exhibit excellent features as fast oxide-ion conductor via an interstitial oxygen mechanism. These new Ba-containing materials were designed to present a more open framework to enhance oxygen conduction. The citrate-nitrate soft-chemistry technique was used to synthesize such structural perovskite-type materials, followed by annealing in air at moderate temperatures (1150 °C). The subtleties of their crystal structures were investigated from neutron powder diffraction (NPD) data. They crystallize in the orthorhombic Pbca space group. Interstitial O3 oxygen atoms were identified by difference Fourier maps in the NaCl layer of the K2NiF4 structure. At variance with the parent compound, conspicuous oxygen vacancies were found at the O2-type oxygen atoms for x = 0.2, corresponding to the axial positions of the InO6 octahedra. The short O2-O3 distances and the absence of steric impediments suggest a dual oxygen-interstitial mechanism for oxide-ion conduction in these materials. Conductivity measurements show that the activation energy values are comparable to those typical of ionic conductors working by simple vacancy mechanisms (~1 eV). The increment of the total conductivity for x = 0.2 can be due to the mixed mechanism driving both oxygen vacancies and interstitials, which is original for these potential electrolytes for solid-oxide fuel cells.

For the development of next-generation lithium batteries, major research effort is made to enable a reversible lithium metal anode by the use of solid electrolytes. However, the fundamentals of the solid-solid interface and especially the processes that take place under current load are still not well characterized. By measuring pressure-dependent electrode kinetics, we explore the electrochemo-mechanical behavior of the lithium metal anode on the garnet electrolyte Li6.25Al0.25La3Zr2O12. Because of the stability against reduction in contact with the lithium metal, this serves as an optimal model system for kinetic studies without electrolyte degradation. We show that the interfacial resistance becomes negligibly small and converges to practically 0 Ω·cm2 at high external pressures of several 100 MPa. To the best of our knowledge, this is the smallest reported interfacial resistance in the literature without the need for any interlayer. We interpret this observation by the concept of constriction resistance and show that the contact geometry in combination with the ionic transport in the solid electrolyte dominates the interfacial contributions for a clean interface in equilibrium. Furthermore, we show that-under anodic operating conditions-the vacancy diffusion limitation in the lithium metal restricts the rate capability of the lithium metal anode because of contact loss caused by vacancy accumulation and the resulting pore formation near the interface. Results of a kinetic model show that the interface remains morphologically stable only when the anodic load does not exceed a critical value of approximately 100 μA·cm-2, which is not high enough for practical cell setups employing a planar geometry. We highlight that future research on lithium metal anodes on solid electrolytes needs to focus on the transport within and the morphological instability of the metal electrode. Overall, the results help to develop a deeper understanding of the lithium metal anode on solid electrolytes, and the major conclusions are not limited to the Li|Li6.25Al0.25La3Zr2O12 interface.